EP3050950B1 - New use of sulfonated polymers - Google Patents

New use of sulfonated polymers Download PDF

Info

Publication number
EP3050950B1
EP3050950B1 EP15153521.8A EP15153521A EP3050950B1 EP 3050950 B1 EP3050950 B1 EP 3050950B1 EP 15153521 A EP15153521 A EP 15153521A EP 3050950 B1 EP3050950 B1 EP 3050950B1
Authority
EP
European Patent Office
Prior art keywords
use
preferably
sulfonated polymer
grams
polymer according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP15153521.8A
Other languages
German (de)
French (fr)
Other versions
EP3050950A1 (en
Inventor
Laura Jane Caufield
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to EP15153521.8A priority Critical patent/EP3050950B1/en
Publication of EP3050950A1 publication Critical patent/EP3050950A1/en
Application granted granted Critical
Publication of EP3050950B1 publication Critical patent/EP3050950B1/en
Application status is Active legal-status Critical
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials characterised by their shape or physical properties
    • C11D17/04Detergent materials characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • C11D17/045Multi-compartment
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions
    • C11D11/0005Special cleaning and washing methods
    • C11D11/0011Special cleaning and washing methods characterised by the objects to be cleaned
    • C11D11/0023"Hard" surfaces
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/26Organic compounds containing nitrogen
    • C11D3/33Amino carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/378(Co)polymerised monomers containing sulfur, e.g. sulfonate

Description

    TECHNICAL FIELD
  • The present invention is in the field of automatic dishwashing. In particular, it relates to the use of sulfonated polymers to provide starch removal benefits.
  • BACKGROUND OF THE INVENTION
  • The automatic dishwashing detergent formulator is continuously looking for ways to improve the performance of detergents. Items placed in a dishwasher to be washed are usually stained with different kinds of soils. Starchy soils are particularly difficult to remove. The problem is more acute when the detergent is phosphate free, see for example WO2011151190 .
  • Sulfonated polymers are used in automatic dishwashing to avoid filming and spotting on the washed items thereby improving the shine of the washed items.
  • SUMMARY OF THE INVENTION
  • The present invention is based on the use of a sulfonated polymer in an automatic dishwashing detergent composition. It has been unexpectedly found that the sulfonated polymer improves the removal of starchy soils from dishware in the presence of soft water. Preferably the composition comprises more than 0.8, more preferably more than 1 and especially 1.2 or more grams of sulfonated polymer. Preferably, the sulfonated polymer comprises 2-acrylamido-2-methylpropane sulfonic acid monomers For the purpose of this invention "dishware" encompasses tableware and cookware and anything that it is usually washed in an automatic dishwasher. By "soft water" is herein meant water having a hardness of less than 50 ppm and especially less than 20 ppm of CaCO3.
  • For the purpose of this invention a "sulfonated polymer" is a polymer comprising sulphur in any of its forms. The "sulfonated polymer" of the invention preferably comprises carboxyl groups.
  • The composition for the use of the invention is sometimes herein referred to as "the composition of the invention".
  • The composition herein is preferably phosphate free. By "phosphate-free" is herein understood that the composition comprises less than 1%, preferably less than 0.1% by weight of the composition of phosphate.
  • The composition comprises an organic complexing agent. It comprises preferably greater than 4 to 9 and especially greater than 4.5 to 8 grams of complexing agent. This level of complexing agent favours the removal of bleachable stains. For the purpose of this invention a "complexing agent" is a compound capable of binding polyvalent ions such as calcium, magnesium, lead, copper, zinc, cadmium, mercury, manganese, iron, aluminium and other cationic polyvalent ions to form a water-soluble complex. The complexing agent has a logarithmic stability constant ([log K]) for Ca2+ of at least 5, preferably at least 6. The stability constant, log K, is measured in a solution of ionic strength of 0.1, at a temperature of 25° C.
  • The complexing agent is preferably selected from the group consisting of methyl-glycine-diacetic acid (MGDA), its salts and derivatives thereof, glutamic-N,N- diacetic acid (GLDA), its salts and derivatives thereof, iminodisuccinic acid (IDS), its salts and derivatives thereof, carboxy methyl inulin, its salts and derivatives thereof and mixtures thereof. Especially preferred complexing agent for use herein is selected from the group consisting of MGDA and salts thereof, especially preferred for use herein is the three sodium salt of MGDA.
  • The composition comprises a bleach. Preferably the composition of the invention comprises from about 1 to about 3 grams of bleach, preferably sodium percarbonate. Preferably the composition also comprises a bleach activator, in particular TAED, and a metal bleach catalyst, in particular a manganese bleach catalyst. Also preferred are compositions comprising a crystal growth inhibitor, in particular 1-hydroxyethylidene 1,1-diphosphonic acid (HEDP) and preferably a non-ionic surfactant.
  • It has been observed that some phosphate-free automatic dishwashing compositions can leave a coloured film on stainless steel items. This problem is avoided when the composition of the invention is free of citrate, thus preferred for use herein are citrate free compositions.
  • Preferably, the composition of the invention has a pH equal or greater than 9 to 12, more preferably equal or greater than 10 to 11.5 as measured in 1% weight aqueous solution in distilled water at 20°C.
  • Preferably the composition of the present invention has a reserve alkalinity of 10 or greater, preferably 12 or greater, most preferably 14 or greater. "Reserve alkalinity", as used herein refers to, the ability of an automatic dishwashing composition to maintain an alkali pH in the presence of acid. This is relative to the ability of an automatic dishwashing composition to have sufficient alkali in reserve to deal with any added acid -coming from the water and/or the soils on the dishware- while maintaining the pH.
  • More specifically, it is defined as the grams of NaOH per 100 cc's, exceeding pH 9.5, in product. The reserve alkalinity for a solution is determined in the following manner.
  • A pH meter (for example An Orion Model 720A) with a Ag/AgCl electrode (for example an Orion sure flow Electrode model 9172BN) is standardized using pH 7 and pH 10 buffers. A 1% solution of the composition to be tested is prepared in distilled water. The weight of the sample is noted. The pH of the 1% solution is measured and the solution is titrated down to pH 9.5 using a solution of 0.2N HCL. The reserve alkalinity is calculated in the following fashion: Reserve Alkalinity = ml HCl × Normality of HCl × 4 ' / Weight of Sample Aliquot Titrated * Equivalent weight of NaOH in the % NaOH equation,
    Figure imgb0001
    derived from: % NaOH = ml HCl × Normality of HCl × Equiv . Weight NaOH × 100 / 1000 × Weight of Sample Aliquot Titrated
    Figure imgb0002
  • Preferably, the composition of the invention is in unit-dose form. By "unit-dose form" is herein meant that the composition is provided in a form sufficient to provide enough detergent for one wash. Suitable unit dose forms include tablets, sachets, capsules, pouches, etc. Preferred for use herein are compositions in unit-dose form wrapped in water-soluble material, for example polyvinyl alcohol. The detergent composition of the invention preferably weighs from 10 to 25 grams, more preferably from about 10 to about 20 grams. This weight range fits comfortable in a dishwasher dispenser. Even although this range amount to a low amount of detergent, the detergent has been formulated in a way that provides all the benefits mentioned herein above.
  • DETAILED DESCRIPTION OF THE INVENTION
  • The present invention relates to the use of a sulfonated polymer in an automatic dishwashing composition to provide starch removal benefits, i.e., the removal of soils containing starch, such as pasta, porridge, etc.
  • Detergent composition
  • The detergent composition of the invention can be presented in unit-dose form and it can be in any physical form including solid, liquid and gel form. The composition of the invention is very well suited to be presented in the form of a multi-compartment pack, more in particular a multi-compartment pack comprising compartments with compositions in different physical forms, for example a compartment comprising a composition in solid form and another compartment comprising a composition in liquid form. The composition is preferably enveloped by a water-soluble film such as polyvinyl alcohol. The composition comprises a sulfonated polymer and optionally but preferably a complexing agent, bleach, crystal growth inhibitor, non-ionic surfactant, etc.
  • The composition of the invention preferably has a pH as measured in 1% weight aqueous solution in distilled water at 20°C of from about 9 to about 12, more preferably from about 10 to less than about 11.5 and especially from about 10.5 to about 11.5.
  • The composition of the invention preferably has a reserve alkalinity of from about 10 to about 20, more preferably from 12 to 18 at a pH of 9.5 as measured in NaOH with 100 grams of product at 20°C.
  • Sulfonated polymer
  • The polymer is used in any suitable amount from about 0.1% to about 30%, preferably from 0.5% to about 20%, more preferably from 1% to 10% by weight of the composition. The composition of the invention comprises at least 0.8 gram, preferably at least 1 gram, more preferably at least 1.2 grams of sulfonated polymer and preferably less than 5 grams of sulfonated polymer. Sulfonated/carboxylated polymers are particularly suitable for the composition of the invention.
  • Suitable sulfonated/carboxylated polymers described herein may have a weight average molecular weight of less than or equal to about 100,000 Da, or less than or equal to about 75,000 Da, or less than or equal to about 50,000 Da, or from about 3,000 Da to about 50,000, preferably from about 5,000 Da to about 45,000 Da.
  • As noted herein, the sulfonated/carboxylated polymers may comprise (a) at least one structural unit derived from at least one carboxylic acid monomer having the general formula (I):
    Figure imgb0003
    wherein R1 to R4 are independently hydrogen, methyl, carboxylic acid group or CH2COOH and wherein the carboxylic acid groups can be neutralized; (b) optionally, one or more structural units derived from at least one nonionic monomer having the general formula (II):
    Figure imgb0004
    wherein R5 is hydrogen, C1 to C6 alkyl, or C1 to C6 hydroxyalkyl, and X is either aromatic (with R5 being hydrogen or methyl when X is aromatic) or X is of the general formula (III):
    Figure imgb0005
    wherein R6 is (independently of R5) hydrogen, C1 to C6 alkyl, or C1 to C6 hydroxyalkyl, and Y is O or N; and at least one structural unit derived from at least one sulfonic acid monomer having the general formula (IV):
    Figure imgb0006
    wherein R7 is a group comprising at least one sp2 bond, A is O, N, P, S or an amido or ester linkage, B is a mono- or polycyclic aromatic group or an aliphatic group, each t is independently 0 or 1, and M+ is a cation. In one aspect, R7 is a C2 to C6 alkene. In another aspect, R7 is ethene, butene or propene.
  • Preferred carboxylic acid monomers include one or more of the following: acrylic acid, maleic acid, itaconic acid, methacrylic acid, or ethoxylate esters of acrylic acids, acrylic and methacrylic acids being more preferred. Preferred sulfonated monomers include one or more of the following: sodium (meth) allyl sulfonate, vinyl sulfonate, sodium phenyl (meth) allyl ether sulfonate, or 2-acrylamido-methyl propane sulfonic acid. Preferred non-ionic monomers include one or more of the following: methyl (meth) acrylate, ethyl (meth) acrylate, t-butyl (meth) acrylate, methyl (meth) acrylamide, ethyl (meth) acrylamide, t-butyl (meth) acrylamide, styrene, or α-methyl styrene.
  • Preferably, the polymer comprises the following levels of monomers: from about 40 to about 90%, preferably from about 60 to about 90% by weight of the polymer of one or more carboxylic acid monomer; from about 5 to about 50%, preferably from about 10 to about 40% by weight of the polymer of one or more sulfonic acid monomer; and optionally from about 1% to about 30%, preferably from about 2 to about 20% by weight of the polymer of one or more non-ionic monomer. An especially preferred polymer comprises about 70% to about 80% by weight of the polymer of at least one carboxylic acid monomer and from about 20% to about 30% by weight of the polymer of at least one sulfonic acid monomer.
  • The carboxylic acid is preferably (meth)acrylic acid. The sulfonic acid monomer is preferably one of the following: 2-acrylamido methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3-methacrylamido-2-hydroxypropanesulfonic acid, allysulfonic acid, methallysulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzensulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrene sulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethylacrylamid, sulfomethylmethacrylamide, and water soluble salts thereof. The unsaturated sulfonic acid monomer is most preferably 2-acrylamido-2-propanesulfonic acid (AMPS).
  • Preferred commercial available polymers include: Alcosperse 240, Aquatreat AR 540 and Aquatreat MPS supplied by Alco Chemical; Acumer 3100, Acumer 2000, Acusol 587G and Acusol 588G supplied by Rohm & Haas; Goodrich K-798, K-775 and K-797 supplied by BF Goodrich; and ACP 1042 supplied by ISP technologies Inc. Particularly preferred polymers are Acusol 587G and Acusol 588G supplied by Rohm & Haas.
  • In the polymers, all or some of the carboxylic or sulfonic acid groups can be present in neutralized form, i.e. the acidic hydrogen atom of the carboxylic and/or sulfonic acid group in some or all acid groups can be replaced with metal ions, preferably alkali metal ions and in particular with sodium ions.
  • Complexing agent
  • A complexing agent is a material capable of sequestering hardness ions, particularly calcium and/or magnesium. The composition of the invention preferably comprises greater than 4 to 10 grams, more preferably greater than 4.5 to 8 grams of a complexing agent. The complexing agent is preferably selected from the group consisting of methyl-glycine-diacetic acid, its salts and derivatives thereof, glutamic-N,N-diacetic acid, its salts and derivatives thereof, iminodisuccinic acid, its salts and derivatives thereof, carboxy methyl inulin, its salts and derivatives thereof and mixtures thereof. Especially preferred complexing agent for use herein is a salt of MGDA, in particular the three sodium salt of MGDA.
  • Bleach
  • The composition of the invention preferably comprises from 1 to 3, preferably from 1.2 to 2.8 and especially from 1.5 to 2.5 grams of bleach.
  • Inorganic and organic bleaches are suitable for use herein. Inorganic bleaches include perhydrate salts such as perborate, percarbonate, perphosphate, persulfate and persilicate salts. The inorganic perhydrate salts are normally the alkali metal salts. The inorganic perhydrate salt may be included as the crystalline solid without additional protection. Alternatively, the salt can be coated. Suitable coatings include sodium sulphate, sodium carbonate, sodium silicate and mixtures thereof. Said coatings can be applied as a mixture applied to the surface or sequentially in layers.
    Alkali metal percarbonates, particularly sodium percarbonate is the preferred bleach for use herein. The percarbonate is most preferably incorporated into the products in a coated form which provides in-product stability.
    Potassium peroxymonopersulfate is another inorganic perhydrate salt of utility herein.
  • Typical organic bleaches are organic peroxyacids, especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid, and diperoxyhexadecanedioc acid. Mono- and diperazelaic acid, mono- and diperbrassylic acid are also suitable herein. Diacyl and Tetraacylperoxides, for instance dibenzoyl peroxide and dilauroyl peroxide, are other organic peroxides that can be used in the context of this invention.
  • Further typical organic bleaches include the peroxyacids, particular examples being the alkylperoxy acids and the arylperoxy acids. Preferred representatives are (a) peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxy acids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxycaproic acid[phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinates, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassylic acid, the diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-dioic acid, N,N-terephthaloyldi(6-aminopercaproic acid).
  • Preferably, the level of bleach in the composition of the invention is from about 0 to about 10%, more preferably from about 0.1 to about 5%, even more preferably from about 0.5 to about 3% by weight of the composition.
  • Bleach Activators
  • Bleach activators are typically organic peracid precursors that enhance the bleaching action in the course of cleaning at temperatures of 60° C and below. Bleach activators suitable for use herein include compounds which, under perhydrolysis conditions, give aliphatic peroxoycarboxylic acids having preferably from 1 to 12 carbon atoms, in particular from 2 to 10 carbon atoms, and/or optionally substituted perbenzoic acid. Suitable substances bear O-acyl and/or N-acyl groups of the number of carbon atoms specified and/or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), decanoyloxybenzoic acid (DOBA), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran and also triethylacetyl citrate (TEAC). If present the composition of the invention comprises from 0.1 to 2, preferably from 0.2 to 1 grams of bleach activator, preferably TAED.
  • Bleach Catalyst
  • The composition herein preferably contains a bleach catalyst, preferably a metal containing bleach catalyst. More preferably the metal containing bleach catalyst is a transition metal containing bleach catalyst, especially a manganese or cobalt-containing bleach catalyst.
    Bleach catalysts preferred for use herein include the manganese triazacyclononane and related complexes ( US-A-4246612 , US-A-5227084 ); Co, Cu, Mn and Fe bispyridylamine and related complexes ( US-A-5114611 ); and pentamine acetate cobalt(III) and related complexes( US-A-4810410 ). A complete description of bleach catalysts suitable for use herein can be found in WO 99/06521 , pages 34, line 26 to page 40, line 16.
  • Manganese bleach catalysts are preferred for use in the composition of the invention. Especially preferred catalyst for use here is a dinuclear manganese-complex having the general formula:
    Figure imgb0007
    wherein Mn is manganese which can individually be in the III or IV oxidation state; each x represents a coordinating or bridging species selected from the group consisting of H2O, O22-, O2-, OH-, HO2-, SH-, S2-, >SO, Cl-, N3-, SCN-, RCOO-, NH2- and NR3, with R being H, alkyl or aryl, (optionally substituted); L is a ligand which is an organic molecule containing a number of nitrogen atoms which coordinates via all or some of its nitrogen atoms to the manganese centres; z denotes the charge of the complex and is an integer which can be positive or negative; Y is a monovalent or multivalent counter-ion, leading to charge neutrality, which is dependent upon the charge z of the complex; and q = z/[charge Y].
  • Preferred manganese-complexes are those wherein x is either CH3COO- or O2 or mixtures thereof, most preferably wherein the manganese is in the IV oxidation state and x is O2-. Preferred ligands are those which coordinate via three nitrogen atoms to one of the manganese centres, preferably being of a macrocyclic nature. Particularly preferred ligands are:
  1. (1) 1,4,7-trimethyl-1,4,7-triazacyclononane, (Me-TACN); and
  2. (2) 1,2,4,7-tetramethyl-1,4,7-triazacyclononane, (Me-Me TACN).
  • The type of counter-ion Y for charge neutrality is not critical for the activity of the complex and can be selected from, for example, any of the following counter-ions: chloride; sulphate; nitrate; methylsulphate; surfactant anions, such as the long-chain alkylsulphates, alkylsulphonates, alkylbenzenesulphonates, tosylate, trifluoromethylsulphonate, perchlorate (ClO4 -), BPh4 -, and PF6 -' though some counter-ions are more preferred than others for reasons of product property and safety.
  • Consequently, the preferred manganese complexes useable in the present invention are:
    1. (I) [(Me-TACN)MnIV(µ-0)3MnIV(Me-TACN)]2+(PF6 -)2
    2. (II) [(Me-MeTACN)MnIV(µ-0)3MnIV(Me-MeTACN)]2+(PF6 -)2
    3. (III) [(Me-TACN)MnIII(µ-0)(µ-OAc)2MnIII(Me-TACN)]2+(PF6 -)2
    4. (IV) [(Me-MeTACN)MnIII(µ-0)(µ-OAc)2MnIII(Me-MeTACN)]2+(PF6 -)2
    which hereinafter may also be abbreviated as:
    1. (I) [MnIV 2(µ-0)3(Me-TACN)2](PF6)2
    2. (II) [MnIV 2(µ-0)3(Me-MeTACN)2](PF6)2
    3. (III) [MnIII 2(µ-0)(µ-OAc)2(Me-TACN)2](PF6)2
    4. (IV) [MnIII 2(µ-0)(µ-0Ac)2(Me-TACN)2](PF6)2
  • The structure of I is given below:
    Figure imgb0008
    abbreviated as [MnIV 2(µ-0)3(Me-TACN)2](PF6)2.
  • The structure of II is given below:
    Figure imgb0009
    abbreviated as [MnIV 2(µ-0)3(Me-MeTACN)2](PF6)2.
  • It is of note that the manganese complexes are also disclosed in EP-A-0458397 and EP-A-0458398 as unusually effective bleach and oxidation catalysts. In the further description of this invention they will also be simply referred to as the "catalyst".
  • Preferably the composition of the invention comprises from 0.001 to 1, more preferably from 0.002 to 0.01 grams of bleach catalyst. Preferably the bleach catalyst is a manganese bleach catalyst.
  • Inorganic builder
  • The composition of the invention preferably comprises an inorganic builder. Suitable inorganic builders are selected from the group consisting of carbonate, silicate and mixtures thereof. Especially preferred for use herein is sodium carbonate. Preferably the composition of the invention comprises from 1 to 8, more preferably from 2 to 6 and especially from 3 to 5 grams of sodium carbonate.
  • Surfactant
  • Surfactants suitable for use herein include non-ionic surfactants, preferably the compositions are free of any other surfactants. Traditionally, non-ionic surfactants have been used in automatic dishwashing for surface modification purposes in particular for sheeting to avoid filming and spotting and to improve shine. It has been found that non-ionic surfactants can also contribute to prevent redeposition of soils.
  • Preferably the composition of the invention comprises a non-ionic surfactant or a non-ionic surfactant system, more preferably the non-ionic surfactant or a non-ionic surfactant system has a phase inversion temperature, as measured at a concentration of 1% in distilled water, between 40 and 70°C, preferably between 45 and 65°C. By a "non-ionic surfactant system" is meant herein a mixture of two or more non-ionic surfactants. Preferred for use herein are non-ionic surfactant systems. They seem to have improved cleaning and finishing properties and better stability in product than single non-ionic surfactants.
  • Phase inversion temperature is the temperature below which a surfactant, or a mixture thereof, partitions preferentially into the water phase as oil-swollen micelles and above which it partitions preferentially into the oil phase as water swollen inverted micelles. Phase inversion temperature can be determined visually by identifying at which temperature cloudiness occurs.
  • The phase inversion temperature of a non-ionic surfactant or system can be determined as follows: a solution containing 1% of the corresponding surfactant or mixture by weight of the solution in distilled water is prepared. The solution is stirred gently before phase inversion temperature analysis to ensure that the process occurs in chemical equilibrium. The phase inversion temperature is taken in a thermostable bath by immersing the solutions in 75 mm sealed glass test tube. To ensure the absence of leakage, the test tube is weighed before and after phase inversion temperature measurement. The temperature is gradually increased at a rate of less than 1°C per minute, until the temperature reaches a few degrees below the pre-estimated phase inversion temperature. Phase inversion temperature is determined visually at the first sign of turbidity.
  • Suitable nonionic surfactants include: i) ethoxylated non-ionic surfactants prepared by the reaction of a monohydroxy alkanol or alkyphenol with 6 to 20 carbon atoms with preferably at least 12 moles particularly preferred at least 16 moles, and still more preferred at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol; ii) alcohol alkoxylated surfactants having a from 6 to 20 carbon atoms and at least one ethoxy and propoxy group. Preferred for use herein are mixtures of surfactants i) and ii).
  • Another suitable non-ionic surfactants are epoxy-capped poly(oxyalkylated) alcohols represented by the formula:

            R1O[CH2CH(CH3)O]x[CH2CH2O]y[CH2CH(OH)R2]     (I)

    wherein R1 is a linear or branched, aliphatic hydrocarbon radical having from 4 to 18 carbon atoms; R2 is a linear or branched aliphatic hydrocarbon radical having from 2 to 26 carbon atoms; x is an integer having an average value of from 0.5 to 1.5, more preferably about 1; and y is an integer having a value of at least 15, more preferably at least 20.
  • Preferably, the surfactant of formula I, at least about 10 carbon atoms in the terminal epoxide unit [CH2CH(OH)R2]. Suitable surfactants of formula I, according to the present invention, are Olin Corporation's POLY-TERGENT® SLF-18B nonionic surfactants, as described, for example, in WO 94/22800, published October 13, 1994 by Olin Corporation.
  • Amine oxides surfactants are useful for use in the composition of the invention. Preferred are C10-C18 alkyl dimethylamine oxide, and C10-18 acylamido alkyl dimethylamine oxide.
  • Surfactants may be present in amounts from 0.1 to 10, more preferably from 0.5 to 5 and especially from 0.8 to 3 grams.
  • Enzymes
  • In describing enzyme variants herein, the following nomenclature is used for ease of reference: Original amino acid(s):position(s):substituted amino acid(s). Standard enzyme IUPAC 1-letter codes for amino acids are used.
  • Proteases
  • Suitable proteases include metalloproteases and serine proteases, including neutral or alkaline microbial serine proteases, such as subtilisins (EC 3.4.21.62) as well as chemically or genetically modified mutants thereof. Suitable proteases include subtilisins (EC 3.4.21.62), including those derived from Bacillus, such as Bacillus lentus, B. alkalophilus, B. subtilis, B. amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii.
  • Especially preferred proteases for the detergent of the invention are polypeptides demonstrating at least 90%, preferably at least 95%, more preferably at least 98%, even more preferably at least 99% and especially 100% identity with the wild-type enzyme from Bacillus lentus, comprising mutations in one or more, preferably two or more and more preferably three or more of the following positions, using the BPN' numbering system and amino acid abbreviations as illustrated in WO00/37627 , which is incorporated herein by reference:V68A, N87S, S99D, S99SD, S99A, S101G, S101M, S103A, V104N/I, G118V, G118R, S128L, P129Q, S130A, Y167A, R170S, A194P, V205I and/or M222S.
  • Most preferably the protease is selected from the group comprising the below mutations (BPN' numbering system) versus either the PB92 wild-type (SEQ ID NO:2 in WO 08/010925 ) or the subtilisin 309 wild-type (sequence as per PB92 backbone, except comprising a natural variation of N87S).
    1. (i) G118V + S128L + P129Q + S130A
    2. (ii) S101M + G118V + S128L + P129Q + S130A
    3. (iii) N76D + N87R + G118R + S128L + P129Q + S130A + S188D + N248R
    4. (iv) N76D + N87R + G118R + S128L + P129Q + S130A + S188D + V244R
    5. (v) N76D + N87R + G118R + S128L + P129Q + S130A
    6. (vi) V68A + N87S + S101G + V104N
  • Suitable commercially available protease enzymes include those sold under the trade names Savinase®, Polarzyme®, Kannase®, Ovozyme®, Everlase® and Esperase® by Novozymes A/S (Denmark), those sold under the tradename Properase®, Purafect®, Purafect Prime®, Purafect Ox®, FN3®, FN4®, Excellase®, Ultimase® and Purafect OXP® by Genencor International, those sold under the tradename Opticlean® and Optimase® by Solvay Enzymes, those available from Henkel/ Kemira, namely BLAP.
  • Preferred levels of protease in the product of the invention include from about 0.1 to about 10, more preferably from about 0.5 to about 7 and especially from about 1 to about 6 mg of active protease.
  • Amylases
  • Preferred enzyme for use herein includes alpha-amylases, including those of bacterial or fungal origin. Chemically or genetically modified mutants (variants) are included. A preferred alkaline alpha-amylase is derived from a strain of Bacillus, such as Bacillus licheniformis, Bacillus amyloliquefaciens, Bacillus stearothermophilus, Bacillus subtilis, or other Bacillus sp., such as Bacillus sp. NCIB 12289, NCIB 12512, NCIB 12513, DSM 9375 (USP 7,153,818 ) DSM 12368, DSMZ no. 12649, KSM AP1378 ( WO 97/00324 ), KSM K36 or KSM K38 ( EP 1,022,334 ). Preferred amylases include:
    1. (a) the variants described in US 5,856,164 and WO99/23211 , WO 96/23873 , WO00/60060 and WO 06/002643 , especially the variants with one or more substitutions in the following positions versus the AA560 enzyme listed as SEQ ID No. 12 in WO 06/002643 :
      9, 26, 30, 33, 82, 37, 106, 118, 128, 133, 149, 150, 160, 178, 182, 186, 193, 195, 202, 214, 231, 256, 257, 258, 269, 270, 272, 283, 295, 296, 298, 299, 303, 304, 305, 311, 314, 315, 318, 319, 320, 323, 339, 345, 361, 378, 383, 419, 421, 437, 441, 444, 445, 446, 447, 450, 458, 461, 471, 482, 484, preferably that also contain the deletions of D183* and G184*.
    2. (b) variants exhibiting at least 95% identity with the wild-type enzyme from Bacillus sp.707 (SEQ ID NO:7 in US 6,093, 562 ), especially those comprising one or more of the following mutations M202, M208, S255, R172, and/or M261. Preferably said amylase comprises one of M202L or M202T mutations.
  • Suitable commercially available alpha-amylases include DURAMYL®, LIQUEZYME®, TERMAMYL®, TERMAMYL ULTRA®, NATALASE®, SUPRAMYL®, STAINZYME®, STAINZYME PLUS®, POWERASE®, FUNGAMYL® and BAN® (Novozymes A/S, Bagsvaerd, Denmark), KEMZYM® AT 9000 Biozym Biotech Trading GmbH Wehlistrasse 27b A-1200 Wien Austria, RAPIDASE®, PURASTAR®, ENZYSIZE®, OPTISIZE HT PLUS® and PURASTAR OXAM® (Genencor International Inc., Palo Alto, California) and KAM® (Kao, 14-10 Nihonbashi Kayabacho, 1-chome, Chuo-ku Tokyo 103-8210, Japan). Amylases especially preferred for use herein include NATALASE®, STAINZYME®, STAINZYME PLUS®, POWERASE® and mixtures thereof.
  • The product of the invention comprises from 0.001 to 0.01 grams of active amylase.
  • Additional Enzymes
  • Additional enzymes suitable for use in the product of the invention can comprise one or more enzymes selected from the group comprising hemicellulases, cellulases, cellobiose dehydrogenases, peroxidases, proteases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, mannanases, pectate lyases, keratinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, β-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, amylases, and mixtures thereof.
  • Preferably, the protease and/or amylase of the product of the invention are in the form of granulates, the granulates comprise less than 29% of sodium sulfate by weight of the granulate or the sodium sulfate and the active enzyme (protease and/or amylase) are in a weight ratio of less than 4:1.
  • Crystal growth inhibitor
  • Crystal growth inhibitors are materials that can bind to calcium carbonate crystals and prevent further growth of species such as aragonite and calcite.
  • Especially preferred crystal growth inhibitor for use herein is HEDP (1-hydroxyethylidene 1,1-diphosphonic acid). Preferably, the composition of the invention comprises from 0.01 to 1, more preferably from 0.05 to 0.8 grams of a crystal growth inhibitor, preferably HEDP.
  • Metal Care Agents
  • Metal care agents may prevent or reduce the tarnishing, corrosion or oxidation of metals, including aluminium, stainless steel and non-ferrous metals, such as silver and copper. Preferably the composition of the invention comprises from 0.001 to 0.01, more preferably from 0.002 to 0.009 grams, preferably the metal care agent is benzo triazole (BTA).
  • Glass Care Agents
  • Glass care agents protect the appearance of glass items during the dishwashing process. Preferably the composition of the invention comprises from 0.001 to 1, more preferably from 0.002 to 0.5 grams of a glass care agent, preferably the glass care agent is a zinc salt.
  • The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm".
  • EXAMPLES
  • Two dual-compartment automatic dishwashing pouches were made comprising the ingredients detailed herein below automatic dishwashing compositions (Composition 1 and Composition 2). The pouches were made of polyvinyl alcohol (Monosol 8630 available from Kuraray) with the solid and liquid components in different compartments.
    Ingredients (grams of active material) Composition 1 Composition 2
    Solid compartment
    Sodium carbonate 4.00 2.80
    MGDA 5.00 5.00
    Sodium percarbonate 2.00 1.80
    Acusol 588 0.40 1.20
    HEDP 0.10 0.10
    Protease 0.034 0.034
    Amylase 0.004 0.004
    Bleach catalyst and bleach activator 0.008 0.008
    Miscellaneous balance to 14.15 balance to 13.61
    Powder only pH 1% w/v 11.02 10.82
    Powder only RA at pH 9.5 in g of NaOH/100g of powder 13.42 9.70
    Liquid compartment
    Lutensol TO7 0.89 0.89
    Plurafac SLF-180 0.84 0.84
    Miscellaneous balance to 2.18 balance to 2.18
  • MGDA
    Tri-sodium salt of methyl glycine diacetic acid
    Amylase
    Stainzyme plus ® supplied by Novozymes
    Protease
    Ultimase ® supplied by DuPont
    Bleach activator
    TAED (Tetraacetylethylenediamine)
    Bleach catalyst
    Manganese bleach catalyst
    HEDP
    1-hydroxyethylidene 1,1-diphosphonic acid
    Plurafac SLF-180
    Nonionic surfactant supplied by BASF
    Lutensol TO7
    Nonionic surfactant supplied by BASF
    RA
    Reserve alkalinity
    Cleaning tests
  • Compositions 1 and 2 were compared for their cleaning performance using CFT tiles (Center For Testmaterials BV. Stoomloggerweg 11, 3133 KT Vlaardingen, the Netherlands), which are stained melamine dishwasher monitors that discriminate the performance of the product to remove enzyme sensitive stains among others.
  • Two tiles per wash of each stain are placed on the top rack of a Miele 1022 dishwashing machine, additional 50g of IKW frozen ballast (prepared according to the IKW method) are added at the beginning of the wash. The inlet water is artificially softened water (through an ion exchange column) with a total level of 10 CaCO3ppm. The cycle used was R-50°C (no prewash). The test is repeated three more times using new tiles each time. At the end the tiles are evaluated using a computer aided image analysis to assign a stain removal index, having a continuous scale from 0 to a 100, where 0% is unwashed and 100% is a complete removal of the stain.
    Internal data Composition 1 Composition 2
    Sulphonated polymer level 0.4g 1.2g
    DM77 Mixed starch, coloured 58.4 74.5 s
    DM376 Triple soiled corn starch 25.9 45.5 s
  • The data shows that the higher level of sulphonated polymer is enhancing the removal of starchy stains.
  • Claims (13)

    1. Use of a sulfonated polymer in an automatic dishwashing detergent composition, the composition comprising an organic complexing agent, bleach and from 0.001 to 0.01 grams of active amylase, for the removal of starch-containing soils from dishware in automatic dishwashing using soft water having a hardness of less than 50 ppm of CaCO3.
    2. Use of a sulfonated polymer according to claim 1 wherein the composition comprises at least 0.8 gram of the sulfonated polymer.
    3. Use of a sulfonated polymer according to any of claims 1 or 2 wherein the detergent composition is phosphate-free.
    4. Use of a sulfonated polymer according to the preceding claim wherein the composition comprises at least 4 grams of the complexing agent.
    5. Use of a sulfonated polymer according to any of the preceding claims wherein the detergent composition comprises a bleach catalyst.
    6. Use of a sulfonated polymer according to any of the preceding claims wherein the bleach catalyst is manganese based.
    7. Use of a sulfonated polymer according to any of the preceding claims wherein the detergent composition comprises a crystal growth inhibitor.
    8. Use of a sulfonated polymer according to any of the preceding claims wherein the detergent composition comprises a non-ionic surfactant.
    9. Use of a sulfonated polymer according to any of the preceding claims wherein the detergent composition has a pH equal or greater than 9 to 12 as measured in 1% w/v aqueous solution at 20°C.
    10. Use of a sulfonated polymer according to any of the preceding claims wherein the detergent composition has a reserve alkalinity equal or greater than 10 to 20 at a pH of 9.5 as measured in NaOH with 100 grams of product at 20°C.
    11. Use of a sulfonated polymer according to any of the preceding claims wherein the detergent composition is in unit dose form, preferably in the form of a multi-compartment pack.
    12. Use of a sulfonated polymer according to the preceding claim wherein the weight of the unit dose is from 10 to 25 grams.
    13. Use of a sulfonated polymer according to any of the preceding claims wherein the detergent composition comprises:
      a) at least 0.8 grams of the sulfonated polymer
      b) from 4 to 8 grams of a complexing agent, preferably the three sodium salt of MGDA;
      c) from 0.5 to 4 grams of bleach, preferably sodium percarbonate;
      the composition having a pH of from 9 to 12 as measured in 1% weight aqueous solution at 20°C and a reserve alkalinity of from 10 to 20 at a pH of 9.5 as measured in NaOH with 100 grams of product at 20°C;
      and wherein the composition is preferably in unit dose form.
    EP15153521.8A 2015-02-02 2015-02-02 New use of sulfonated polymers Active EP3050950B1 (en)

    Priority Applications (1)

    Application Number Priority Date Filing Date Title
    EP15153521.8A EP3050950B1 (en) 2015-02-02 2015-02-02 New use of sulfonated polymers

    Applications Claiming Priority (3)

    Application Number Priority Date Filing Date Title
    EP15153521.8A EP3050950B1 (en) 2015-02-02 2015-02-02 New use of sulfonated polymers
    JP2017540732A JP2018503732A (en) 2015-02-02 2016-02-01 A new use of sulfonated polymer
    PCT/US2016/015902 WO2016126579A1 (en) 2015-02-02 2016-02-01 New use of sulfonated polymers

    Publications (2)

    Publication Number Publication Date
    EP3050950A1 EP3050950A1 (en) 2016-08-03
    EP3050950B1 true EP3050950B1 (en) 2018-09-19

    Family

    ID=52432754

    Family Applications (1)

    Application Number Title Priority Date Filing Date
    EP15153521.8A Active EP3050950B1 (en) 2015-02-02 2015-02-02 New use of sulfonated polymers

    Country Status (3)

    Country Link
    EP (1) EP3050950B1 (en)
    JP (1) JP2018503732A (en)
    WO (1) WO2016126579A1 (en)

    Families Citing this family (1)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US20180291312A1 (en) * 2017-04-11 2018-10-11 Itaconix Corporation Sulfonated Copolymers For Detergent Composition

    Family Cites Families (31)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    GB2048606B (en) 1979-02-28 1983-03-16 Barr & Stroud Ltd Optical scanning system
    GB8629837D0 (en) 1986-12-13 1987-01-21 Interox Chemicals Ltd Bleach activation
    GB8908416D0 (en) 1989-04-13 1989-06-01 Unilever Plc Bleach activation
    EP0458398B1 (en) 1990-05-21 1997-03-26 Unilever N.V. Bleach activation
    GB9108136D0 (en) 1991-04-17 1991-06-05 Unilever Plc Concentrated detergent powder compositions
    US5576281A (en) 1993-04-05 1996-11-19 Olin Corporation Biogradable low foaming surfactants as a rinse aid for autodish applications
    AT305031T (en) 1994-03-29 2005-10-15 Novozymes As Alkaline amylase from bacellus
    AR000862A1 (en) 1995-02-03 1997-08-06 Novozymes As Variants of an O-amylase, a method for producing the same, a DNA and an expression vector, a cell transformed by dichaestructura DNA and vector, a detergent additive, detergent composition, a composition for laundry and a composition for the removal of
    US6093562A (en) 1996-02-05 2000-07-25 Novo Nordisk A/S Amylase variants
    JP3025627B2 (en) 1995-06-14 2000-03-27 花王株式会社 Alkaline liquefying α- amylase gene
    GB2327947A (en) 1997-08-02 1999-02-10 Procter & Gamble Detergent tablet
    EP2011864B1 (en) 1999-03-31 2014-12-31 Novozymes A/S Polypeptides having alkaline alpha-amylase activity and nucleic acids encoding same
    AU9737398A (en) 1997-10-30 1999-05-24 Novo Nordisk A/S Alpha-amylase mutants
    AU773066B2 (en) 1998-12-18 2004-05-13 Novozymes A/S Subtilase enzymes of the I-S1 and I-S2 sub-groups having an additional amino acid residue in an active site loop region
    US6403355B1 (en) 1998-12-21 2002-06-11 Kao Corporation Amylases
    WO2002010356A2 (en) 2000-07-28 2002-02-07 Henkel Kommanditgesellschaft Auf Aktien Novel amylolytic enzyme extracted from bacillus sp. a 7-7 (dsm 12368) and washing and cleaning agents containing this novel amylolytic enzyme
    JP2002180096A (en) * 2000-12-11 2002-06-26 Matsushita Electric Ind Co Ltd Liquid composition for dishwashing and washing method
    MXPA04004523A (en) * 2001-11-14 2004-08-11 Procter & Gamble Automatic dishwashing composition in unit dose form comprising an anti-scaling polymer.
    JP2003268579A (en) * 2002-03-12 2003-09-25 Kobe Steel Ltd Cleaning liquid for aluminum sheet, cleaning method therefor and cleaning equipment
    JP4303155B2 (en) * 2003-10-31 2009-07-29 ディバーシー・アイピー・インターナショナル・ビー・ヴイ Automatic dishwashing detergent composition
    AU2005259686B2 (en) 2004-07-05 2010-12-23 Novozymes A/S Alpha-amylase variants with altered properties
    GB0522659D0 (en) * 2005-11-07 2005-12-14 Reckitt Benckiser Nv Delivery cartridge
    JP4978068B2 (en) * 2006-06-14 2012-07-18 ライオンハイジーン株式会社 Automatic washing machine detergent composition
    DK2059591T3 (en) 2006-07-18 2012-10-29 Danisco Us Inc Detergent containing a protease variant
    JP5480491B2 (en) * 2008-11-14 2014-04-23 ディバーシー株式会社 Parts box detergent compositions and cleaning method using the same
    US20120067373A1 (en) * 2010-04-15 2012-03-22 Philip Frank Souter Automatic Dishwashing Detergent Composition
    WO2011151190A1 (en) * 2010-06-02 2011-12-08 Henkel Ag & Co. Kgaa Dishwasher products in a compacted form
    ES2555872T3 (en) * 2011-06-15 2016-01-11 Basf Se Polyesters branched sulphonate groups
    JP5806632B2 (en) * 2012-02-28 2015-11-10 株式会社ニイタカ Automatic dishwashing liquid detergent
    PL2662436T3 (en) * 2012-05-11 2018-02-28 The Procter And Gamble Company Detergent composition
    JP6375129B2 (en) * 2014-04-01 2018-08-15 株式会社Adeka The method of washing dishes

    Non-Patent Citations (1)

    * Cited by examiner, † Cited by third party
    Title
    None *

    Also Published As

    Publication number Publication date
    EP3050950A1 (en) 2016-08-03
    WO2016126579A1 (en) 2016-08-11
    JP2018503732A (en) 2018-02-08

    Similar Documents

    Publication Publication Date Title
    CA2435487C (en) Copolymers for preventing glass corrosion
    US8697623B2 (en) Detergent composition
    US20120067373A1 (en) Automatic Dishwashing Detergent Composition
    ES2582589T3 (en) soluble bag
    JP5551621B2 (en) Automatic dishwashing detergent composition
    JP5559707B2 (en) Automatic dishwashing detergent composition
    US8354366B2 (en) Cleaning products
    EP2024475B1 (en) Detergent composition
    WO2003038028A2 (en) Detergent or cleanser that can be dispersed in an essentially sediment-free manner
    JP5551622B2 (en) Automatic dishwashing detergent composition
    ES2401126T3 (en) detergent composition
    ES2646416T3 (en) detergent composition
    JP2013503932A5 (en) Detergent composition
    US20180223016A1 (en) Itaconic acid polymers
    CA2797094C (en) Neutral detergent compositions comprising aminocarboxylic acidifying particles
    EP2166092A1 (en) Detergent composition
    US20140179585A1 (en) Detergent composition with silicate coated bleach
    CA2895786C (en) Multi-compartment water-soluble pack comprising a cleaning composition
    US8431518B2 (en) Detergent composition
    EP2380962B1 (en) Particle
    US20110139182A1 (en) Detergent use
    EP2940116B1 (en) Detergent
    JP5932906B2 (en) Detergent compositions and the use thereof
    JP5620511B2 (en) Detergent composition
    EP2997121B1 (en) Machine dishwash detergent composition

    Legal Events

    Date Code Title Description
    AX Request for extension of the european patent to:

    Extension state: BA ME

    AK Designated contracting states

    Kind code of ref document: A1

    Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

    RBV Designated contracting states (corrected)

    Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

    17P Request for examination filed

    Effective date: 20170202

    INTG Intention to grant announced

    Effective date: 20180322

    AK Designated contracting states

    Kind code of ref document: B1

    Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

    REG Reference to a national code

    Ref country code: GB

    Ref legal event code: FG4D

    REG Reference to a national code

    Ref country code: CH

    Ref legal event code: EP

    REG Reference to a national code

    Ref country code: AT

    Ref legal event code: REF

    Ref document number: 1043278

    Country of ref document: AT

    Kind code of ref document: T

    Effective date: 20181015

    REG Reference to a national code

    Ref country code: IE

    Ref legal event code: FG4D

    REG Reference to a national code

    Ref country code: DE

    Ref legal event code: R096

    Ref document number: 602015016420

    Country of ref document: DE

    REG Reference to a national code

    Ref country code: NL

    Ref legal event code: MP

    Effective date: 20180919

    PG25 Lapsed in a contracting state [announced from national office to epo]

    Ref country code: RS

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20180919

    Ref country code: FI

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20180919

    Ref country code: GR

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20181220

    Ref country code: LT

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20180919

    Ref country code: SE

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20180919

    Ref country code: BG

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20181219

    Ref country code: NO

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20181219

    REG Reference to a national code

    Ref country code: LT

    Ref legal event code: MG4D

    PG25 Lapsed in a contracting state [announced from national office to epo]

    Ref country code: HR

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20180919

    Ref country code: LV

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20180919

    Ref country code: AL

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20180919

    REG Reference to a national code

    Ref country code: AT

    Ref legal event code: MK05

    Ref document number: 1043278

    Country of ref document: AT

    Kind code of ref document: T

    Effective date: 20180919

    PG25 Lapsed in a contracting state [announced from national office to epo]

    Ref country code: IT

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20180919

    Ref country code: RO

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20180919

    Ref country code: CZ

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20180919

    Ref country code: EE

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20180919

    Ref country code: NL

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20180919

    Ref country code: IS

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20190119

    Ref country code: AT

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20180919

    Ref country code: PL

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20180919

    Ref country code: ES

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20180919

    PGFP Annual fee paid to national office [announced from national office to epo]

    Ref country code: GB

    Payment date: 20190130

    Year of fee payment: 5

    Ref country code: DE

    Payment date: 20190122

    Year of fee payment: 5

    PG25 Lapsed in a contracting state [announced from national office to epo]

    Ref country code: SK

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20180919

    Ref country code: SM

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20180919

    Ref country code: PT

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20190119